Distribution Of Atoms Research Articles

Achieving balanced mechanical properties in Fe–0.16C plain low-carbon steel by trimodal microstructure and fine cementite

In the present study, for the first time, a trimodal microstructure (including coarse, fine, and ultrafine ferrite grains) was created in plain low-carbon steel by simple thermomechanical processing including intercritical annealing (at 770 °C, 800 °C, and 830 °C), 75% cold rolling, and finally heat treatment at 550 °C. The results showed that martensite with two different morphologies consisting of lath (low-carbon) and plate (high-carbon) were created in the microstructures of 800-75% and 830-75% sheets due to the non-homogeneous distribution of carbon atoms as a result of not using the homogenization treatment. After the final heat treatment, the samples exhibited trimodal grain size distribution of ferrite including coarse grains (larger than 5 micrometers), fine grains (between 1 and 5 micrometers), and ultrafine grains (UFGs) (smaller than 1 micrometer). The formation of ultrafine grains was ascribed to the presence of martensite with lath morphology in the 800-75% and 830-75% samples. The size of cementite particles in the 770-75%-550 sample was larger than the other two samples (800-75%-550 and 830-75%-550) owing to the presence of martensite phase only with plate morphology in 770-75%-550 steel. Unlike the 800-75%-550 sheet, the entire microstructure of the 770-75%-550 and 830-75%-550 samples had not undergone complete recrystallization and several deformed ferrite grains were still visible in the microstructures. The strength and hardness of the heat-treated sheets was larger than that of the as-received steel due to the presence of fine spherical cementite particles and fine ferrite grains in the microstructure of the heat-treated samples. Based on the obtained results, the 800-75%-550 sample revealed the best combination of strength-ductility-toughness due to trimodal microstructure along with the formation of fine spherical cementite particles. The failure mode of all heat-treated samples was ductile and there were both fine and coarse dimples in the fracture surfaces.

Thermally Activated Delayed Fluorescence Sensitizer with Through‐Space Charge Transfer Manipulated by Atom Distribution for Solution‐Processed Deep‐Blue Multi‐Resonance OLEDs

AbstractOrganic light‐emitting diodes (OLEDs) employing multi‐resonance (MR) emitters have attracted much attention due to their high luminescent efficiency and color purity, however, the development of deep‐blue multi‐resonance OLEDs is hindered by the lack of suitable sensitizers. Here a novel design strategy is reported for thermally activated delayed fluorescence sensitizer with high reverse intersystem crossing (kRISC) and radiative transition (kR) rate by regulating atom distribution of a spatially‐aligned carbazole donor/diphenylpyrimidine acceptor structure to manipulate through‐space charge transfer (CT) process. It is found that diphenylpyrimidine acceptor with 1,3‐position nitrogen atoms is un‐conjugated to bridging phenyl moiety by the conjugation node of pyrimidine, while the acceptor with 1,5‐position nitrogen atoms is conjugated to bridging phenyl through conjugation site, opening through‐bond CT pathway via bridging phenyl besides through‐space CT from spatial donor‐acceptor interactions. As a result, the sensitizer with 1,5‐position nitrogen atoms exhibits enhanced oscillator strength by 3.5 folds and accelerated kR of 3.57 × 107 s−1, while keeping high kRISC of 4.03 × 106 s−1 and high singlet (S1) state (2.88 eV). Solution‐processed OLEDs using the sensitizer and deep‐blue multi‐resonance emitter exhibit efficient narrowband electroluminescence with CIE coordinates of (0.14, 0.13) and EQEmax of 15.6%, representing the state‐of‐the‐art device performance for deep‐blue multi‐resonance OLEDs by solution process.

Structural characterisation of a cyanomesogen by X-ray diffraction and computational methods

The work reports the structural analysis of a cyanomesogen namely, p-cyanobenzylidene p-nonyloxyaniline belonging to the Schiff base class of compounds. It exhibits a partial bilayer/inter-digitated smectic Ad phase and a nematic phase. Polarising Optical Microscopy (POM) and Differential Scanning Calorimetry (DSC) studies have been carried out to study phase sequence and transition temperatures. Micro-structural parameters, like molecular length, spacing, crystallite size, activation energy and micro-strain, have been estimated and pair correlation function (PCF) studies have been done for exhibited mesophases using the X-ray diffraction technique. The study investigated the surface, electronic and optical properties of a compound by computational studies like Density Functional Theory (DFT) and Hirshfeld surface analysis (HSA) methods using the DFT B3LYP/6-311++G(d,p) level basis set. The results reveal that the polarity associated with the polar groups and alkoxy chain lengths, contributes majorly to the mesomorphic characteristics and stability. The Highest Occupied Molecular Orbitals (HOMO) and Lowest Unoccupied Molecular Orbitals (LUMO) analyses of the DFT optimised molecule give electronic and geometrical parameters, atomic charge distribution, polarisability factors which are used to interpret the characteristics of the mesophases and their suitability for electro-optical and non-linear optical applications of the compound in terms of the predicted data.

Anomalous hardening of two-component disordered crystals

The nature of increasing the strength of disordered two-component solid solutions in comparison with materials consisting of atoms of one component is studied. For this purpose, the contribution of extreme fluctuations in the distribution of solution atoms, which create obstacles for the movement of dislocation kinks, is calculated. It is shown that a slow - power - decrease in the probability of large delays on such obstacles leads to anomalous kinetics of kinks. It is accompanied by a slowdown in the movement of dislocations. This may be the reason for the hardening of the material.

Progress and challenges in structural, in situ and operando characterization of single-atom catalysts by X-ray based synchrotron radiation techniques.

Single-atom catalysts (SACs) represent the ultimate size limit of nanoscale catalysts, combining the advantages of homogeneous and heterogeneous catalysts. SACs have isolated single-atom active sites that exhibit high atomic utilization efficiency, unique catalytic activity, and selectivity. Over the past few decades, synchrotron radiation techniques have played a crucial role in studying single-atom catalysis by identifying catalyst structures and enabling the understanding of reaction mechanisms. The profound comprehension of spectroscopic techniques and characteristics pertaining to SACs is important for exploring their catalytic activity origins and devising high-performance and stable SACs for industrial applications. In this review, we provide a comprehensive overview of the recent advances in X-ray based synchrotron radiation techniques for structural characterization and in situ/operando observation of SACs under reaction conditions. We emphasize the correlation between spectral fine features and structural characteristics of SACs, along with their analytical limitations. The development of IMST with spatial and temporal resolution is also discussed along with their significance in revealing the structural characteristics and reaction mechanisms of SACs. Additionally, this review explores the study of active center states using spectral fine characteristics combined with theoretical simulations, as well as spectroscopic analysis strategies utilizing machine learning methods to address challenges posed by atomic distribution inhomogeneity in SACs while envisaging potential applications integrating artificial intelligence seamlessly with experiments for real-time monitoring of single-atom catalytic processes.

Synthesis of group-IV ternary and binary semiconductors using epitaxy of GeH3Cl and SnH4

Ge1−x−ySixSny alloys were grown on Ge buffers via reactions of SnH4 and GeH3Cl. The latter is a new CVD source designed for epitaxial development of group-IV semiconductors under low thermal budgets and CMOS-compatible conditions. The Ge1−x−ySixSny films were produced at very low temperatures between 160 and 200 °C with 3%–5% Si and ∼5%–11% Sn. The films were characterized using an array of structural probes that include Rutherford backscattering, x-ray photoelectron spectroscopy, high-resolution x-ray diffraction, scanning transmission electron microscopy, and atomic force microscopy. These studies indicate that the films are strained to Ge and exhibit defect-free microstructures, flat surfaces, homogeneous compositions, and sharp interfaces. Raman was used to determine the compositional dependence of the vibrational modes indicating atomic distributions indistinguishable from those obtained when using high-order Ge hydrides. For a better understanding of the growth mechanisms, a parallel study was conducted to investigate the GeH3Cl applicability for synthesis of binary Ge1−ySny films. These grew strained to Ge, but with reduced Sn compositions and lower thicknesses relative to Ge1−x−ySixSny. Bypassing the Ge buffers led to Ge1−ySny-on-Si films with compositions and thicknesses comparable to Ge1−ySny-on-Ge; but their strains were mostly relaxed. Efforts to increase the concentration and thickness of Ge1−ySny-on-Si resulted in multiphase materials containing large amounts of interstitial Sn. These outcomes suggest that the incorporation of even small Si amounts in Ge1−x−ySixSny might compensate for the large Ge–Sn mismatch by lowering bond strains. Such an effect reduces strain energy, enhances stability, promotes higher Sn incorporation, and increases critical thickness.

QM9star, two Million DFT-computed Equilibrium Structures for Ions and Radicals with Atomic Information

Ions and radicals serve as key intermediates in molecular transformation, with their chemical properties being essential for understanding and predicting reaction reactivity and selectivity. In this data descriptor, we report a quantum chemical dataset named QM9star, comprising cations, anions, and radicals. This dataset is derived from the molecular structures of the QM9 dataset, created by removing terminal hydrogens followed by optimization using B3LYP-D3(BJ)/6-311 + G(d,p) level of density functional theory. The QM9star dataset includes approximately 1.9 million cations, anions, and radicals, along with 120 kilo neutral molecules prior to hydrogen removal. Each entry encompasses both molecular and atomic information: representative global properties include orbital energies, vibrational frequencies, etc., while local properties cover aspects such as charges and spin densities at each atomic site. The QM9star dataset not only serves as a comprehensive source of quantum chemical information for intermediates but also offers insights into the principle of atomic property distribution. We anticipate that these data will aid in machine learning studies related to chemical intermediates and contribute to the molecular representation learning.

Functional Design Of Peroral Delivery Systems Based On Polymethylsesquoxane Hydrogels For The Therapy Of Iron Deficiency Anemia

Anemia is a prevalent circulatory system illness that is severely harmful to patients. The development of novel oral delivery systems for iron compounds with enhanced biopharmaceutical properties is vital considering the severe side effects associated with oral medication use. We believe incorporating iron compounds to polymethylsilsesquioxane hydrogels is a promising approach. According to previously published materials, such a system should have great biocompatibility and a capacity for iron compounds, and it may be able to release contents into the intestine. This study investigated polymethysilsesquioxane hydrogels with varying silicate unit concentrations. Potential iron-containing medicines were iron(III) chloride (FeCl3∙6H2O)) and iron(II) D-gluconate. All hydrogels were found to have nearly 100% sorption activity for a saturated solution of FeCl3∙6H2O (0.27 M) during the experiment, but only around 30% sorption capacity was found for a saturated solution of D-gluconate (0.24 M). A specific field of study was the distribution of iron atoms within hydrogels. It has been established that the largest regions devoid of iron atoms are observed in a hydrogel with a maximum quantity of inorganic units. The outcomes provide opportunities for the precise engineering of polymer matrix structures for iron compound delivery.

Structural Features Investigation of a Highly Dispersed NiO–SiO<sub>2</sub> Catalyst by X-Ray Analysis of the Atomic Pair Distribution Function

In the present work NiO and NiO–SiO2 were investigated by X-ray diffraction and radial atomic pair distribution methods. By X-ray diffraction method, it was determined that the NiO particle sizes have coherent scattering region of more than 100 nm, while the NiO–SiO2 sample has a particle size of about 2–3 nm. At the same time, full-profile Rietveld simulation does not describe the effects observed on diffraction: the asymmetry of peaks, the appearance of an additional shoulder of peak 111 in the area of small angles, so the radial atomic pair distribution method was used to analyze the structure. During the simulation of the experimental atomic pair distribution curve, 3 different models were used: pure NiO, a mixture of NiO and Ni2SiO4, and a modified NiO model with Si embedded in the lattice. The latter model was created based on the assumption of silicon incorporation into the NiO structure, which can be evidenced by X-ray diffraction data. According to the results of radial atomic pair distribution modeling it is the latter model that gives the best description of the observed effects: significantly increased unit cell parameter, compared to the sample without SiO2 addition, as well as decreased metal cation–oxygen distances in the structure, while cation–cation distances are increased.

Gas jet target with controllable density via throat diameter of conical nozzle

A supersonic gas jet has been a special target in the ultraintense laser interaction field due to its controllable atomic density distribution. This work investigates the spatial atomic density distribution in argon gas jets ejected from conical nozzles with different throat diameters. Both experiment and simulation results show that the atomic density and its distribution can be controlled by changing the throat diameter of the conical nozzle. The quantitative dependence of atomic density on the throat diameter under different backing pressures is obtained. It also agrees with that from the one-dimensional gas dynamics model. However, it is noted that for a large throat diameter at a high gas backing pressure, a radial saddle-shaped atomic density profile is demonstrated experimentally within a few millimeters away from the nozzle outlet. The results are helpful to optimize the density profile in gas-jet targets and to understand the effect of the throat diameter of the conical nozzle on cluster size in Hagena scaling law.

Deciphering Surface Ligand Density of Colloidal Semiconductor Nanocrystals: Shape Matters.

Surface chemistry of colloidal semiconductor nanocrystals (NCs) is of paramount importance because it profoundly impacts their physical and chemical properties, processing, and performance. Herein, we report the effect of the shape of ZnS NCs in terms of nanodots, nanorods, and nanoplatelets (NPL) on the surface ligand density (LD) of the commonly used oleylamine (OLA) ligand by combining three experimental quantification techniques (e.g., thermogravimetric analysis-differential scanning calorimetry, 1H nuclear magnetic resonance spectroscopy, and inductively coupled plasma-optical emission spectrometry) with the semiempirical molecular dynamics (MD) simulations. Consistent results on the surface LD derived by the aforementioned three independent techniques were obtained, presenting an ascending order of LDdots < LDrods < LDNPLs. MD simulations reveal that the highest LD for ZnS NPLs can be attributed to their extremely flat and uniform surfaces with regular distribution of surface Zn atoms for the OLA molecules to achieve parallel and tight stacking, while for ZnS nanodots and nanorods, their surfaces may have staggered arrangement and multisteps, making it unlikely for the OLA ligand to adopt the tight ligand stacking mode. The finding revealed in this work not only sheds light on the constitution of the molecule ligand shell of NCs, which is helpful for their rational morphology control, but also provides an additional and important knob for tuning their chemical functionality.

Mechanisms for forming methylglyoxal complexes with benzene and ethanol molecules. Nonempirical calculations

The formation mechanism of methylglyoxal monomers, dimers, trimers, methylglyoxal+benzene, and methylglyoxal+ethanol complexes was investigated using the density functional theory (DFT) approach and the B3LYP/6-311++G(d, p) functional set. Methylglyoxal has two C=O stretching vibrations, and in solvents, the intensity of the first C=O vibration band increased sharply, and the intensity of the second C=O vibration band decreased. This is due to the C=O···H hydrogen bond formed between methylglyoxal+benzene/ethanol solvents. Also, the calculations showed that among the molecules of methyglyoxal+benzene/ethanol mainly weak interactions, i.e. Van der Waals interactions, play a dominant role. Calculations are shown the complex formation energy increases as the number of molecules increases, but the average hydrogen bond energy corresponding to each bond remains unchanged. Also, the DFT method was used to study molecular structure, quantum chemical parameters such as Mulliken atomic charge distribution, atoms in molecules (AIM), reduced density gradient (RDG) and noncovalent interaction (NCI), electron localization functions (ELF), and localized orbital locator (LOL).

Gradient distribution of cations in rhabdophane La0.27Y0.73PO4·nH2O nanoparticles

The structure of gradient rhabdophane nanoparticles of variable composition (La,Y)PO4·nH2O obtained by precipitation is considered. According to the data of HAADF TEM and EDX mapping using the Abel inversion procedure, it was shown that there is an inhomogeneous distribution of yttrium and lanthanum atoms in the particles from the central part to the periphery. At the same time, the nominal composition of both individual nanoparticles and the entire sample meets the value specified during synthesis within the error of the method – La0.27Y0.73PO4·nH2O. According to SAXS data, it was determined that in the particles of (La,Y)PO4·nH2O, there is a redistribution of scattering densities, which is caused by an increase in the fraction of YPO4 in the peripheral region of the particles. The observed effect of the distribution of cations over the particle made it possible to determine the size of the gradient layer, which reaches 50 % of the total particle size.

Novel Amorphous Nitride‐Halide Solid Electrolytes with Enhanced Performance for All‐Solid‐State Batteries

Solid electrolytes (SEs) in all‐solid‐state batteries (ASSBs) are garnering considerable attention for their potential applications in next‐generation energy storage systems. Amorphous SEs with dual‐anion hold great promise for achieving favorable performance, such as high ionic conductivity and good compatibility with electrodes within ASSBs. Here, we discover a family of amorphous nitride‐halide SEs, Li3xMClyNx (M = Ta or La, 1 ≤ 3x ≤ 1.4, y = 5 or 3), which can achieve ionic conductivities up to 7.34 mS cm‒1 at 30 °C. The amorphous properties and local structures are investigated using powder X‐ray diffraction, cryogenic transmission electron microscopy, and atomic pair distribution function analysis. Impressively, ASSBs employing amorphous Li3xTaCl5Nx have demonstrated good performance at high rates and charging voltages, as well as at low temperature.

Novel Amorphous Nitride-Halide Solid Electrolytes with Enhanced Performance for All-Solid-State Batteries.

Solid electrolytes (SEs) in all-solid-state batteries (ASSBs) are garnering considerable attention for their potential applications in next-generation energy storage systems. Amorphous SEs with dual-anion hold great promise for achieving favorable performance, such as high ionic conductivity and good compatibility with electrodes within ASSBs. Here, we discover a family of amorphous nitride-halide SEs, Li3xMClyNx (M = Ta or La, 1 ≤ 3x ≤ 1.4, y = 5 or 3), which can achieve ionic conductivities up to 7.34 mS cm‒1 at 30 °C. The amorphous properties and local structures are investigated using powder X-ray diffraction, cryogenic transmission electron microscopy, and atomic pair distribution function analysis. Impressively, ASSBs employing amorphous Li3xTaCl5Nx have demonstrated good performance at high rates and charging voltages, as well as at low temperature.

Insight into the mechanism of H2O promoted CaCO3 decomposition in CO2 atmosphere

Calcium looping is one of the most promising CO2 capture technology. The flus gas during the calcination stage of the calcium looping contains both CO2 and H2O. However, the effect of H2O on the decomposition of carbonation in the CO2 atmosphere remains inconclusive. This study employed the Reactive Force Field molecular dynamics (ReaxFF-MD) simulations to investigate the influence of H2O on the decomposition of calcium carbonate in a CO2 atmosphere. The TGA experiments demonstrated that H2O increases the decomposition rate of calcium carbonate and also reduces the reaction temperature. Subsequently, the effects of varying CO2 and H2O concentrations on the decomposition of calcium carbonate were examined using ReaxFF-MD simulations. The simulation results for calcium carbonate decomposition, with the addition of CO2 and H2O, aligned with the experimental trends, verifying the reliability of the models. By tracking and labeling carbon, oxygen and hydrogen atom sources in the simulation, the decomposition, carbonation and hydrolysis reaction network for the CaCO3 decomposition in CO2 atmosphere was systematically constructed. Analysis of the chemical reactions and atomic distribution indicated that H2O primarily facilitates calcium carbonate decomposition by generating HCO3− through surface hydrolysis, which reduces the activation energy of the reaction. Moreover, the hydroxyl groups formed by hydrolysis compete with atmospheric CO2 for active sites on CaO, further inhibiting the carbonation reaction and increasing the calcination rate.

Density-Density Correlation Spectra of Ultracold Bosonic Gas Released from a Deep 1D Optical Lattice.

Density-density correlation analysis is a convenient diagnostic tool to reveal the hidden order in the strongly correlated phases of ultracold atoms. We report on a study of the density-density correlations of ultracold bosonic atoms which were initially prepared in a Mott insulator (MI) state in one-dimensional optical lattices. For the atomic gases released from the deep optical lattice, we extracted the normalized density-density correlation function from the atomic density distributions of freely expanded atomic clouds. Periodic bunching peaks were observed in the density-density correlation spectra, as in the case of higher-dimensional lattices. Treating the bosonic gas within each lattice well as a subcondensate without quantum tunneling, we simulated the post-expansion density distribution along the direction of the 1D lattice, and the calculated density-density correlation spectra agreed with our experimental observations.

Field Ion Microscopy of Tungsten Nano-Tips Coated with Thin Layer of Epoxy Resin

This paper presents an analysis of the field ion emission mechanism of tungsten–epoxy nanocomposite emitters and compares their performance with that of tungsten nano-field emitters. The emission mechanism is described using the theory of induced conductive channels. Tungsten emitters with a radius of 70 nm were fabricated using electrochemical polishing and coated with a 20 nm epoxy resin layer. Characterization of the emitters, both before and after coating, was performed using electron microscopy and energy-dispersive X-ray spectroscopy (EDS). The Tungsten nanocomposite emitter was tested using a field ion microscope (FIM) in the voltage range of 0–15 kV. The FIM analyses revealed differences in the emission ion density distributions between the uncoated and coated emitters. The uncoated tungsten tips exhibited the expected crystalline surface atomic distribution in the FIM images, whereas the coated emitters displayed randomly distributed emission spots, indicating the formation of induced conductive channels within the resin layer. The atom probe results are consistent with the FIM findings, suggesting that the formation of conductive channels is more likely to occur in areas where the resin surface is irregular and exhibits protrusions. These findings highlight the distinct emission mechanisms of both emitter types.

Mechanisms of nodule formation on Ni-Pt targets during sputtering

Ni-Pt alloys are employed in the formation of Ni-Pt silicide to facilitate contact and interconnection functions in semiconductor devices. However, the formation of nodules on the Ni-Pt target during sputtering results in a reduced deposition rate and abnormal discharge, significantly impacting the film quality. This study investigates the nodule formation mechanism on the surface of Ni-Pt targets during sputtering, utilizing field-emission scanning electron microscopy (FE-SEM), energy-dispersive spectroscopy (EDS), and electron backscatter diffraction (EBSD). The findings reveal that defects and inclusion areas in the target exhibit a slower sputtering rate compared to normal areas, ultimately leading to nodule formation. Notably, platinum-rich layers were observed on the surfaces of nodules, particularly those exceeding a height of 100 μm. The variations in target surface concentration, angular distribution, and sputter yield of Ni and Pt atoms, coupled with the blocking effect of the lateral areas of nodules, contribute to the formation and compositional variation of the Pt-rich layers on the nodule surfaces.

Theoretical exploration of binary mixtures derived from hydrogen bond liquid crystalline soft materials for optical device fabrication

Binary mixtures are obtained from 4-Nitrobenzaldehyde (NBA), 4-(heptyloxy)benzoic acid (7OBA) and 4-(octyloxy)benzoic acid (8OBA) abbreviated as NBA + 7OBA and NBA + 8OBA. Density Functional Theory (DFT) is used to optimize the resultant molecular structures. HOMO–LUMO and NBO analysis are adapted in obtaining the charge transfer phenomenon of the binaries. Molecular electrostatic Potential (MEP) analysis reveals the active sites of liquid crystals. Atomic charge distribution of the binary mixture is investigated theoretically. Topological analysis is carried out to understand the intermolecular interaction between non mesogenic NBA and mesogenic precursors along with nonlinear optical properties. The results obtained are correlated with the experimental data obtained.